EP2279213A1 - Nouveau mécanisme de réticulation pour des revêtements organiques minces sur la base de la réaction de synthèse de la dihydropyridine de hantzsch - Google Patents

Nouveau mécanisme de réticulation pour des revêtements organiques minces sur la base de la réaction de synthèse de la dihydropyridine de hantzsch

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Publication number
EP2279213A1
EP2279213A1 EP09751338A EP09751338A EP2279213A1 EP 2279213 A1 EP2279213 A1 EP 2279213A1 EP 09751338 A EP09751338 A EP 09751338A EP 09751338 A EP09751338 A EP 09751338A EP 2279213 A1 EP2279213 A1 EP 2279213A1
Authority
EP
European Patent Office
Prior art keywords
coating composition
grams
cross
reaction
beta
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09751338A
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German (de)
English (en)
Other versions
EP2279213B1 (fr
Inventor
Brian D. Bammel
Thomas S. Ii Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2279213A1 publication Critical patent/EP2279213A1/fr
Application granted granted Critical
Publication of EP2279213B1 publication Critical patent/EP2279213B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C09D191/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31688—Next to aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31699—Ester, halide or nitrile of addition polymer

Definitions

  • This invention relates generally to cross-linking reactions in organic coating resins and, more particularly, to cross-linking reactions based on the Hantzsch dihydropyridine synthesis reaction.
  • Cross-linking reactions for cross-linking coating resins are known in the art. Cross-linking can enhance the properties of coated substrates. These properties include mechanical, physical, aesthetic, and corrosion resistance.
  • One difficulty with current cross-linking reactions is that they often require high processing temperatures which limits their usefulness for certain substrates.
  • many of the cross-linking reactions require non-aqueous solutions or are reversible, which presents performance problems.
  • this invention provides a cross-linking reaction process and system that operates at lower temperatures in aqueous systems and that is irreversible.
  • the process relies on a method for formation of Hantzsch Dihydropyridines as the cross- linking group.
  • the system uses two equivalents of beta-keto esters on the resin, such as those provided by acetoacetoxyethyl methacrylate, one equivalent of aldehyde and one equivalent of ammonia or a primary amine to produce a Hantzsch Dihydropyridine.
  • Figure 1 is a schematic of the proposed Hantzsch Dihydropyridine cross- linking mechanism according to the present invention.
  • the present invention is directed toward a cross-linking mechanism for cross-linking adjacent polymer chains in a coating resin.
  • Cross-linking reactions have been utilized in the past for coating resins, however they suffer from a need for high heat of reaction, need for harsh conditions, non-aqueous systems, or reversibility.
  • the present invention provides for a cross-linking reaction that operates at low temperatures relative to other cross-linking reactions, occurs in aqueous solutions, and is irreversible.
  • the present cross-linking reaction improves the chemical properties, mechanical properties, barrier properties, physical properties and corrosion resistance of the coating resin.
  • the present reaction can be used to cause cross-linking in thin organic coatings, organic coatings, passivate rinses, sealing rinses, adhesives, and sealants, by way of example.
  • the present invention is directed toward treatment of bare metal surfaces meaning that the metal surface has not been pre-treated with any metal phosphate solutions, chrome-containing rinses, or any other passivating treatments.
  • Metal surfaces that benefit from the process of the present invention include steel, cold rolled steel, hot rolled steel, stainless steel, aluminum, steel coated with zinc metal or zinc alloys such as electrogalvanized steel, galvalume®, galvanneal, and hot-dipped galvanized steel.
  • the metal surface has been cleaned and degreased prior to treatment according to the present invention.
  • Cleaning of metal surfaces is well known in the art and can include mild or strongly alkaline cleaners. Examples of two alkaline cleaners include Parco® Cleaner ZX-I and Parco® Cleaner 315 both available from Henkel Surface Technologies. Following cleaning the surface is preferably rinsed with water prior to treatment according to the present invention.
  • the Hantzsch dihydropyridine/pyridine synthesis reaction allows the preparation of a dihydropyridine derivative by a condensation reaction of an aldehyde with two equivalents of a beta-keto ester, such as provided by the pendant chains after incorporation of acetoacetoxyethyl methacrylate into the resin, in the presence of ammonia or a primary amine.
  • a subsequent oxidation or dehydrogenation leads to a pyridine 3,5-dicarboxylate.
  • Ammonia or a variety of primary amines are useful in present invention.
  • Examples include ammonia, amino acids, diamines, and other molecules with primary amine groups. It has been found that the amine levels can be very high, far in excess of the number of beta-keto ester groups on the resin without interfering with the Hantzsch Dihydropyridine reaction.
  • aldehydes may be used in the present invention including, only by way of example, formaldehyde, salicylaldehyde, cinnamaldehyde, glucose, vanillin, glyoxal, and glyoxylic acid.
  • the amount of aldehyde is closely tailored to the level of resin beta-keto ester sites.
  • the cross-linking solution includes from 0.1 to 1.5 equivalents of aldehyde per 2 equivalents of beta-keto ester groups on the resin, more preferably from 0.5 to 1.1 aldehyde equivalents per 2 equivalents of beta-keto ester groups on the resin.
  • a series of resins were prepared having as the pendent chains with beta- keto ester functions acetoacetoxyethyl methacrylate (AAEM). This is just one of the possible pendant chains that could be used in the process of the present invention.
  • AAEM acetoacetoxyethyl methacrylate
  • An organic coating resin was prepared as described below, it is designated as resin 3272-096.
  • the resin includes as monomers: acetoacetoxyethyl methacrylate (AAEM), n-butyl methacrylate, styrene, methyl methacrylate, 2-ethylhexyl acrylate, and ADD APT PolySurf HP which is a mixture of methacrylated mono and di-phosphate ester.
  • AAEM acetoacetoxyethyl methacrylate
  • styrene methyl methacrylate
  • 2-ethylhexyl acrylate 2-ethylhexyl acrylate
  • ADD APT PolySurf HP Another potential source for phosphates in all resins prepared according to the present invention is Ebecryl 168 from Radcure Corporation.
  • the total monomer distribution in the resin was as follows: 20.00% AAEM, 12.50% n-butyl methacrylate, 15.00% styrene, 27.50% methyl methacrylate, 20.00% 2-ethylhexyl acrylate, and 5.00% ADD APT PolySurf HP.
  • the resin polymerization reaction was run under N 2 with stirring and a heat set point of 80 0 C.
  • the initial charge to the reaction vessel was 241.10 grams of deionized (DI) water, 2.62 grams of ammonium lauryl sulfate (Rhodapon L-22 EP), and 2.39 grams of ferrous sulfate 0.5% FeSC ⁇ H 2 O (3ppm).
  • This initial charge was put into the reaction vessel at time zero and heating to the set point was begun.
  • a reactor seed comprising a combination of 5.73 grams of DI water, 0.90 grams of non-ionic surfactant Tergitol 15-S-20, 0.13 grams of Rhodapon L-22 EP, 2.15 grams of n-butyl methacrylate, 2.57 grams of styrene, 4.74 grams of methyl methacrylate, 3.48 grams of 2-ethylhexyl acrylate, 3.41 grams of acetoacetoxyethyl methacrylate (AAEM), and 0.85 grams of ADD APT PolySurf HP was added to the reaction vessel and heating to the set point was continued for another 15 minutes.
  • an initial initiator charge was added to the vessel comprising 0.32 grams of HOCH 2 SO 2 Na, 4.68 grams of DI water, 0.45 grams of tert- butylhydroperoxide, and an additional 4.54 grams of DI water and the temperature was maintained at the set point for another 30 minutes. Then the monomer and initiator co- feeds were added to the vessel over a three hour period with the temperature maintained at the set point.
  • the monomer co-feed was 106.92 grams of DI water, 17.10 grams of Tergitol 15-S-20, 2.49 grams of Rhodapon L-22 EP, 40.89 grams of n-butyl methacrylate, 48.83 grams of styrene, 89.97 grams of methyl methacrylate, 66.10 grams of 2-ethylhexyl acrylate, 64.77 grams of AAEM, and 16.19 grams of ADD APT PolySurf HP.
  • the initiator co-feed was 0.97 grams Of HOCH 2 SO 2 Na, 14.03 grams of DI water, 1.39 grams of tert-butylhydroperoxide, and an additional 13.61 grams of DI water.
  • the chaser charge was 0.32 grams of HOCH 2 SO 2 Na, 4.88 grams of DI water, 0.46 grams of tert- butylhydroperoxide, and an additional 4.54 grams of DI water.
  • the vessel was then held at the set point for one hour and 30 minutes. Then the cool down from the set point was begun and continued for 2 hours until the temperature was 38° C. Then the buffer co-feed was added to the vessel.
  • the buffer co-feed was 5.19 grams of ammonium hydroxide (28%) and 18.48 grams of DI water.
  • non-ionic surfactant stabilizers that could be used in place of Tergitol 15-S-20, which is a secondary alcohol ethoxylate, in this resin and all resins in accordance with the present invention are other non-ionic stabilizers having a hydrophilic lipophilic balance of from 15 to 18.
  • these stabilizers include: other secondary alcohol ethoxylates such as Tergitol 15-S-15; blends of ethoxylates such as Abex 2515; alkyl polyglycol ether such as Emulsogen LCN 118 or 258; tallow fatty alcohol ethoxylate such as Genapol T 200 and T 250; isotridecyl alcohol ethoxylates such as Genapol X 158 and X 250; tridecyl alcohol ethoxylates such as Rhodasurf BC-840; and oleyl alcohol ethoxylates such as Rhoadsurf ON-877.
  • other secondary alcohol ethoxylates such as Tergitol 15-S-15
  • blends of ethoxylates such as Abex 2515
  • alkyl polyglycol ether such as Emulsogen LCN 118 or 258
  • tallow fatty alcohol ethoxylate such as Genapol T 200 and T 250
  • An organic coating resin was prepared as described below, it is designated as resin 3272-103.
  • the resin includes as monomers: acetoacetoxyethyl methacrylate (AAEM), n-butyl methacrylate, styrene, methyl methacrylate, 2-ethylhexyl acrylate, and ADD APT PolySurf HP which is a mixture of methacrylated mono and di-phosphate ester.
  • the total monomer distribution in the resin was as follows: 20.00% AAEM, 12.50% n- butyl methacrylate, 15.00% styrene, 27.50% methyl methacrylate, 20.00% 2-ethylhexyl acrylate, and 5.00% ADD APT PolySurf HP.
  • the resin polymerization reaction was run under N 2 with stirring and a heat set point of 80 0 C.
  • the initial charge to the reaction vessel was 286.10 grams of DI water, 2.47 grams of Rhodapon L-22 EP. This initial charge was put into the reaction vessel at time zero and heating to the set point was begun.
  • a reactor seed comprising a combination of 5.44 grams of DI water, 0.85 grams of Tergitol 15-S-20, 0.12 grams of Rhodapon L-22 EP, 2.04 grams of n-butyl methacrylate, 2.44 grams of styrene, 4.49 grams of methyl methacrylate, 3.30 grams of 2- efhylhexyl acrylate, 3.24 grams of acetoacetoxyethyl methacrylate (AAEM), and 0.81 grams of ADD APT PolySurf HP was added to the reaction vessel and heating to the set point was continued for another 15 minutes.
  • an initial initiator charge was added to the vessel comprising 4.79 grams of DI water and 0.21 grams of (NH -S ) 2 S 2 Os and the temperature was maintained at 80° C for another 30 minutes. Then the monomer and initiator co-feeds were added to the vessel over a three hour period with the temperature maintained at the set point.
  • the monomer co-feed was 103.36 grams of DI water, 16.15 grams of Tergitol 15-S-20, 2.35 grams of Rhodapon L-22 EP, 38.81 grams of n-butyl methacrylate, 46.34 grams of styrene, 85.38 grams of methyl methacrylate, 62.73 grams of 2-ethylhexyl acrylate, 61.47 grams of AAEM, and 15.37 grams of ADD APT PolySurf HP.
  • the initiator co-feed was 14.36 grams of DI water and 0.64 grams of (NHU) 2 S 2 O 8 . After the three hours a chaser charge was added to the vessel over a 30 minute period.
  • the chaser charge was 0.35 grams of ascorbic acid, 4.65 grams of DI water, 0.44 grams of tert-butylhydroperoxide, an additional 4.56 grams of DI water, and 2.39 grams of ferrous sulfate 0.5% FeSO 4 7H 2 O (3p ⁇ m).
  • the vessel was then held at the set point for one hour and 30 minutes. Then the cool down was begun and continued for 2 hours until the temperature was 38° C. Then the buffer co-feed was added to the vessel.
  • the buffer co- feed was 5.88 grams of ammonium hydroxide (28%) and 18.48 grams of DI water.
  • An organic coating resin was prepared as described below, it is designated as resin 3272-056.
  • the resin includes as monomers: acetoacetoxyethyl methacrylate (AAEM), n-butyl methacrylate, styrene, methyl methacrylate, 2-ethylhexyl acrylate, and ADD APT PoIyS urf HP which is a mixture of methacrylated mono and di -phosphate ester.
  • the total monomer distribution in the resin was as follows: 20.00% AAEM, 12.50% n- butyl methacrylate, 15.00% styrene, 27.50% methyl methacrylate, 20.00% 2-ethylhexyl acrylate, and 5.00% ADD APT PolySurf HP.
  • the resin polymerization reaction was run under N 2 with stirring and a heat set point of 70 0 C.
  • the initial reactor charge was 241.01 grams of DI water, and 2.62 grams of Rhodapon L-22 EP (ammonium lauryl sulfate).
  • the second reactor charge was 2.39 grams of ferrous sulfate 0.5% FeSO 4 7H 2 O (3 ppm).
  • the two initiator co-feeds were 1.62 grams Of HOCH 2 SO 2 Na in 23.38 grams of DI water and 2.31 grams of tert-butylhydroperoxide in 22.69 grams of DI water.
  • the monomer co-feed was 114.41 grams of DI water, 18.00 grams of Tergitol 15-S-20 (secondary alcohol ethoxylate surfactant), 2.62 grams of Rhodapon L-22 EP, 68.18 grams of AAEM, 43.05 grams of n-butyl methacrylate, 51.39 grams of styrene, 94.70 grams of methyl methacrylate, 69.58 grams of 2-ethylhexyl acrylate, and 17.05 grams of ADD APT PolySurf HP.
  • the neutralizer charge was 6.52 grams of 28% ammonium hydroxide in 18.48 grams of DI water.
  • the process commenced with adding the initial reactor charge to the reaction vessel with stirring for 30 minutes. Then 25 grams of the monomer co-feed was added to the reaction vessel as a seed along with 4 milliliters of each initiator co-feed and the second reactor charge. Then the monomer co-feed was fed into the reaction vessel over a 3 hour period and the initiator co-feeds were fed into the reaction vessel over a 4 hour period. After the final addition of the initiator co-feeds the reaction was run for an additional 40 minutes and then cool down to 38 0 C was begun. After 1 hour and 45 minutes of cool down the neutralizer charge was added to the reaction vessel. [00018] In a first test two coating compositions were prepared to determine if the
  • Hantzsch dihydropyridine reaction could take place in a resin coating composition.
  • the test involved use of resin 3272-096 and either vanillin or salicylaldehyde as the aldehyde source for the reaction.
  • the required amine for the reaction is provided by the Bacote 20® which has a great excess of ammonium to serve as the amine in the reaction.
  • Bacote 20® is one preferred source of ammonium zirconyl carbonate and is available from MEI in Flemington New Jersey. It provides approximately 20% w/w of ZrO 2 .
  • the two test formulas are provided in Table 1 below.
  • the coatings of the present invention can also include processing aids such as waxes which aid in formability of the coated substrates.
  • the coatings were applied at a coating weight of approximately 200 milligrams per square foot (200 milligrams per 929.03 square centimeters) to each panel and then dried to a peak metal temperature of either 200° F (93° C) or 300° F (149° C) and either put directly into the NSS test or first washed with the alkaline cleaner PCl 338 and then put in to the NSS test. A drop in NSS results after pre-treatment with PCl 338 would indicate that the coatings are not alkaline resistant.
  • the coated panels were then tested for corrosion resistance using NSS according to ASTM Bl 17. For each time point multiples of each condition were examined and the percentage of the total surface corroded was determined, averaged and reported below.
  • the alkaline treatment was as follows: a portion of each panel was dipped into a 20% NaOH solution for approximately 1 to 2 minutes and then removed for visual evaluation. The results showed that using PMT of 200 or 250° F (93 or 121° C) provided no resistance to alkaline dip, in fact, the dip removed the entire coating down to bare metal. By way of contrast PMT of 300 or 350° F (149 or 177° C) provided complete resistance to the alkaline treatment. This indicates that the Hantzsch Dihydropyridine reaction may require PMT of from 250 to 300° F (121 to 149° C) for completion using this formulation.
  • Coatings prepared according to the present invention are designed to be applied directly to bare metal substrates without the need for any phosphate or other pre- treatments other than cleaning. They can be applied at any desired coating weight required by the situation, preferably they are applied at a coating weight of from 150 to 400 milligrams per square foot (150 to 400 milligrams per 929.03 square centimeters), more preferably at from 175 to 300 milligrams per square foot (175 to 300 milligrams per 929.03 square centimeters) and most preferably at from 175 to 250 milligrams per square foot (175 to 250 milligrams per 929.03 square centimeters).
  • the coatings of the present invention are dry in place coatings as known in the art and are preferably dried to a peak metal temperature of from 180 to 350° F (82 to 177° C), more preferably to a PMT of from 200 to 325° F (93 to 163° C).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention porte sur un procédé de réticulation destiné à réticuler les chaînes polymères d'une composition de revêtement. Dans un mode de réalisation, le procédé utilise une réaction de synthèse de la dihydropyridine de Hantzsch pour former des produits de réaction comprenant des chaînes d'une résine polymère réticulée ayant des fonctions bêta-cétoester à l’aide d'une source d'aldéhyde et d'une source d'ammoniac ou d'une amine primaire pour former une liaison dihydropyridine permanente entre les fonctions bêta-cétoester. La nouvelle réaction de réticulation peut avoir lieu à des températures plus basses que celles des réactions typiques de réticulation, et peut se produire dans des solutions aqueuses ayant un pH neutre à légèrement alcalin, de 6 à 11. La nouvelle réaction de réticulation apporte de nombreux avantages lors de l’exécution d'une réticulation de chaînes polymères dans des résines de revêtement.
EP20090751338 2008-05-19 2009-05-19 Nouveau mécanisme de réticulation pour des revêtements organiques minces sur la base de la réaction de synthèse de la dihydropyridine de hantzsch Not-in-force EP2279213B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US5436008P 2008-05-19 2008-05-19
PCT/US2009/044457 WO2009143110A1 (fr) 2008-05-19 2009-05-19 Nouveau mécanisme de réticulation pour des revêtements organiques minces sur la base de la réaction de synthèse de la dihydropyridine de hantzsch

Publications (2)

Publication Number Publication Date
EP2279213A1 true EP2279213A1 (fr) 2011-02-02
EP2279213B1 EP2279213B1 (fr) 2015-03-18

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US (2) US8883916B2 (fr)
EP (1) EP2279213B1 (fr)
JP (1) JP5602725B2 (fr)
KR (1) KR20110023860A (fr)
CN (1) CN102066432B (fr)
AU (1) AU2009249220B2 (fr)
BR (1) BRPI0912744A2 (fr)
CA (1) CA2724517C (fr)
ES (1) ES2538787T3 (fr)
RU (1) RU2010151476A (fr)
WO (1) WO2009143110A1 (fr)

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US8241524B2 (en) * 2009-05-18 2012-08-14 Henkel Ag & Co. Kgaa Release on demand corrosion inhibitor composition
JP5616291B2 (ja) * 2010-06-11 2014-10-29 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ ジアルデヒドから製造された５−および６−員環式エナミン化合物からの速硬化性熱硬化性物質
US9441116B2 (en) 2011-10-11 2016-09-13 Rohm And Haas Company Aqueous polymer dispersion
CN102585646B (zh) * 2012-03-02 2014-04-02 淮海工学院 硅丙树脂基海洋防污涂料及其制备方法
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US9896594B2 (en) 2018-02-20
US20150024195A1 (en) 2015-01-22
EP2279213B1 (fr) 2015-03-18
WO2009143110A1 (fr) 2009-11-26
ES2538787T3 (es) 2015-06-24
AU2009249220A1 (en) 2009-11-26
CA2724517C (fr) 2017-04-18
US8883916B2 (en) 2014-11-11
RU2010151476A (ru) 2012-06-27
AU2009249220B2 (en) 2015-05-07
CA2724517A1 (fr) 2009-11-26
KR20110023860A (ko) 2011-03-08
CN102066432B (zh) 2015-07-29
JP5602725B2 (ja) 2014-10-08
BRPI0912744A2 (pt) 2015-10-13
CN102066432A (zh) 2011-05-18
US20110111237A1 (en) 2011-05-12
JP2011521082A (ja) 2011-07-21

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